Why ozonolysis may not increase the hydrophilicity of particles

It is commonly assumed that atmospheric oxidation of hydrocarbon particles or hydrocarbon coatings on particles leads to polar products and increased water uptake, altering atmospheric visibility and increasing the likelihood they will act as cloud condensation nuclei (CCN). We show here through laboratory experiments that increased water uptake depends on the 3-dimensional structure of the particles. Laboratory studies of particles formed during ozonolysis of surface-bound alkenes, present as terminally unsaturated self-assembled monolayers (C8= SAM) on a silica substrate, were carried out at room temperature and 1 atm pressure. SAMs were exposed to ～10¹³ O₃ molecules cm^?3 for 40 min and resultant particles were analyzed using single particle Fourier transform infrared micro-spectroscopy (micro-FTIR) and secondary ion mass spectroscopy (SIMS). Spectroscopy results show that –COOH and other polar groups are formed but are buried inside a hydrophobic shell, consistent with earlier observations (McIntire et al., 2005, Moussa et al., 2009) that water uptake does not increase after reaction of the terminal alkene with O₃. These insights into the 3-D structure of particles formed on oxidation have important implications for the ability of secondary organic aerosols to act as CCN. In addition, the nature of the surface of the particles is expected to determine their uptake into biological systems such as the surface of the lungs.     

The application of profluorescent nitroxides to detect reactive oxygen species derived from combustion-generated particulate matter: Cigarette smoke – A case study

Reactive oxygen species (ROS) and related free radicals are considered to be key factors underpinning the various adverse health effects associated with exposure to ambient particulate matter. Therefore, measurement of ROS is a crucial factor for assessing the potential toxicity of particles. In this work, a novel profluorescent nitroxide, BPEAnit, was investigated as a probe for detecting particle-derived ROS. BPEAnit has a very low fluorescence emission due to inherent quenching by the nitroxide group, but upon radical trapping or redox activity, a strong fluorescence is observed. BPEAnit was tested for detection of ROS present in mainstream and sidestream cigarette smoke. In the case of mainstream cigarette smoke, there was a linear increase in fluorescence intensity with an increasing number of cigarette puffs, equivalent to an average of 101 nmol ROS per cigarette based on the number of moles of the probe reacted. Sidestream cigarette smoke sampled from an environmental chamber exposed BPEAnit to much lower concentrations of particles, but still resulted in a clearly detectible increase in fluorescence intensity with sampling time. It was calculated that the amount of ROS was equivalent to 50 ± 2 nmol per mg of particulate matter; however, this value decreased with ageing of the particles in the chamber. Overall, BPEAnit was shown to provide a sensitive response related to the oxidative capacity of the particulate matter. These findings present a good basis for employing the new BPEAnit probe for the investigation of particle-related ROS generated from cigarette smoke as well as from other combustion sources.     

Effects of agricultural pesticides on the health of Rana pipiens frogs sampled from the field

There is evidence that over the last 30 years, there have been mass declines in diverse geographic locations among amphibian populations due to disease outbreaks. Multiple causes have been suggested to explain this increase in disease incidence. Among these, climate changes, environmental pollution and reduced water quality are gaining attention. Indeed, some chemicals of environmental concerns are known to alter the immune system. It is possible that exposure to these pollutants could alter the immune system of anurans and render them more susceptible to different pathogens. In this study, we sampled Rana pipiens in five different sites near St. Lawrence River (Quebec, Canada) during the months of July and September in 2001. Two of these sites were protected areas, in which low levels of pesticides were detected, while the remaining three sites were located in areas with intensive corn and soybeans cultivations. Our results demonstrated that frogs living in agricultural regions are smaller in size and weight than frogs living in areas with lower levels of pesticides at both sampling times. Moreover, we have observed a significant decrease in the number of splenocytes (cellularity) and the phagocytic activity in frogs sampled in impacted sites. Taken together, these results suggest that frogs living in agricultural regions might be more vulnerable to infections and diseases through their smaller size and alteration of their immune system. Our results also contribute to the overall discussion on factors involved in amphibian declines.     

Automotive Exhaust Emission Levels by Geographic Area and Vehicle Make A Nationwide Survey

Gross average automotive exhaust emissions data collected by the Atlantic Richfield Clean Air Caravan during the summer of 1970 showed only slight geographical variations when the specific makes were ignored. When considering specific makes, significant differences were found on an average emissions basis. Vehicle population—emission distributions showed wide variations in the 50% population levels and in the percent of vehicles with emissions greater than specified values. Hydrocarbon (HC) and carbon monoxide (CO) data are given on a gross basis for the 1970, 1968-69, 1966-67, and pre-1966 model year group vehicles. Average HC and CO emissions and vehicle population-Idle emissions distribution curves are included for specific make vehicles in selected areas.     

Weekday-Weekend Pollutant Studies of the Los Angeles Basin

Pollutant data from the Los Angeles Basin were analyzed for weekday-weekend differences for the smog months of June through September 1972 and 1973. The pollutants investigated were oxidant, NO, NO₂, total hydrocarbons (HC), CO, and particulates. In order to maintain the diurnal variation, the concentration percentiles were calculated for each weekday and weekend hour.     

Turbulent Plume in a Turbulent Cross Flow: Comparison of Wind Tunnel Tests with Field Observations

Plume rise downwind of a large stationary gas turbine was measured in the field and the conditions were then scaled in the laboratory. For the laboratory, the plume exit conditions, wind velocity and temperature profiles, and wind direction were matched. It was found that for high temperature exhaust, the buoyancy is best matched by calculating a dimensionless density difference. With properly calculated buoyancy length scales, the plume trajectories were compared and were found to agree quite well. The probability distributions of the entrainment constant and the average values of the entrapment constant with downwind distance were compared. The field data showed about 15% greater plume rise. The median entrainment constant was about 10% greater for the lab test and the shape of the probability distribution matched very closely.     

Variance Design and Air Pollution Control

Confronted with shortages of low sulfur content residual fuel oil and, consequently, faced with the threat of social and economic upheaval, several air pollution control authorities in the Northeastern states were forced to relax hard-won air quality standards during the winter of 1972. The authorities did so by granting variances to their sulfur content standards for residual fuel oil. This paper examines the institutional characteristics of these variance policies from an economic incentive standpoint. After setting up desirable structural criteria for institutional design of such crisis policies, the authors examine the experience of the winter of 1972 and arrive at policy guidelines which recommend themselves for consideration in future periods of fuel oil shortages.     

Interregional Exchanges of Air Pollution: Model Types and Applications

Regional scale air quality simulation models covering spatial scales of thousands of kilometers are finding increasing applications in studies of acid deposition and other air pollution problems. The purpose of this paper is to familiarize the nonexpert with the characteristics of the major types of interregional air quality models currently in use: Eulerian grid, statistical trajectory, and Lagrangian trajectory. The basic features, advantages, and disadvantages of each of these modeling approaches are summarized, as are the important limitations and problems associated with interregional modeling in general. Typical applications are illustrated using examples from the use of a representative Lagrangian trajectory model, ENAMAP, over the eastern North American area.